Exposure apparatus, exposure method, and device manufacturing method

ABSTRACT

An exposure apparatus exposes a substrate with exposure light via a liquid. The exposure apparatus includes an optical system including an emission surface from which the exposure light is emitted; a liquid supply port that supplies the liquid in order to fill an optical path of the exposure light emitted from the emission surface with the liquid; and a fluid supply port that supplies a fluid including a material capable of changing the specific resistance of the liquid to at least a part of a space around a liquid immersion space that is formed by the liquid.

CROSS-REFERENCE TO RELATED APPLICATION

This is a Divisional application of U.S. application Ser. No.13/228,032, filed Sep. 8, 2011, which is a Continuation application ofInternational Application No. PCT/JP2010/001695, filed on Mar. 10, 2010,which claims priority to U.S. provisional application No. 61/202,533,filed Mar. 10, 2009, the contents of which are incorporated herein byreference.

BACKGROUND

1. Field of the Invention

The present invention relates to an exposure apparatus, an exposuremethod, and a device manufacturing method.

2. Description of Related Art

In exposure apparatuses used in photolithography processes, a liquidimmersion exposure apparatus that exposes a substrate with exposurelight via a liquid, as disclosed in Patent Document (Specification of USPatent Application Publication No. 2007/0139632), for example, is known.

In the liquid immersion exposure apparatus, there is a possibility thatliquid filling the optical path of exposure light is charged. Moreover,there is also a possibility that a member contacting the liquid is alsocharged. Due to the charging, there is a possibility that foreignmaterials may be adsorbed to at least one of the liquid and the member.As a result, there is a possibility that exposure defects may occur, sothat defective devices are produced.

SUMMARY

An object of aspects of the present invention is to provide an exposureapparatus and an exposure method capable of suppressing the occurrenceof exposure defects resulting from charging of liquid or the like.Another object of aspects of the present invention is to provide adevice manufacturing method capable of suppressing the occurrence ofdefective devices.

According to a first aspect of the present invention, there is providedan exposure apparatus that exposes a substrate with exposure light via aliquid, including: an optical system including an emission surface fromwhich the exposure light is emitted; a liquid supply port that suppliesthe liquid in order to fill an optical path of the exposure lightemitted from the emission surface with the liquid; and a fluid supplyport that supplies a fluid including a material capable of changing thespecific resistance of the liquid to at least a part of a space around aliquid immersion space that is formed by the liquid.

According to a second aspect of the present invention, there is providedan exposure apparatus that exposes a substrate with exposure light,including: an optical system including an emission surface from whichthe exposure light is emitted; a first supply port that supplies a firstliquid in order to fill an optical path of the exposure light emittedfrom the emission surface with the first liquid having a first specificresistance; and a second supply port that supplies a second liquidhaving a lower specific resistance than the first liquid to at least apart of a space around a liquid immersion space that is formed by thefirst liquid.

According to a third aspect of the present invention, there is providedan exposure apparatus that exposes a substrate with exposure light via aliquid, including: an optical system including an emission surface fromwhich the exposure light is emitted; a liquid supply port that suppliesthe liquid in order to fill an optical path of the exposure lightemitted from the emission surface with the liquid; a fluid supply portthat supplies a fluid including a material capable of changing thespecific resistance of the liquid; and a fluid recovery port thatrecovers at least some of the fluid from at least a part of a spacearound a liquid immersion space that is formed by the liquid.

According to a fourth aspect of the present invention, there is provideda device manufacturing method including: exposing a substrate using theexposure apparatus according to any one of the first, second, and thirdaspects; and developing the exposed substrate.

According to a fifth aspect of the present invention, there is providedan exposure method including: filling an optical path of exposure lightbetween an emission surface of an optical system and a substrate with aliquid; supplying a liquid including a material capable of changing thespecific resistance of the liquid to at least a part of a space around aliquid immersion space of the liquid, formed on the substrate; andexposing the substrate with the exposure light via the liquid betweenthe emission surface and the substrate.

According to a sixth aspect of the present invention, there is providedan exposure method including: filling an optical path of exposure lightbetween an emission surface of an optical system and a substrate with afirst liquid; supplying a second liquid having a lower specificresistance than the first liquid to at least a part of a space around aliquid immersion space of the first liquid, formed on the substrate; andexposing the substrate with the exposure light via the first liquidbetween the emission surface and the substrate.

According to a seventh aspect of the present invention, there isprovided an exposure method including: filling an optical path ofexposure light between an emission surface of an optical system and asubstrate with a liquid; supplying a fluid including a material capableof changing the specific resistance of the liquid; recovering at leastsome of the fluid from at least a part of a space around a liquidimmersion space of the liquid, formed on the substrate; and exposing thesubstrate with the exposure light via the liquid between the emissionsurface and the substrate.

According to an eighth aspect of the present invention, there isprovided a device manufacturing method including: exposing a substrateusing the exposure apparatus according to any one of the fifth, sixth,and seventh aspects; and developing the exposed substrate.

According to the aspects of the present invention, it is possible tosuppress the occurrence of exposure defects. Moreover, according to thepresent invention, it is possible to suppress the occurrence ofdefective devices.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic configuration diagram showing an example of anexposure apparatus according to a first embodiment.

FIG. 2 is a cross-sectional view showing the vicinity of a terminatingoptical element and a liquid immersion member according to the firstembodiment.

FIG. 3 is a cross-sectional view showing the vicinity of the liquidimmersion member according to the first embodiment.

FIG. 4 is a cross-sectional view showing the vicinity of the liquidimmersion member according to a second embodiment.

FIG. 5 is a cross-sectional view showing the vicinity of the liquidimmersion member according to a third embodiment.

FIG. 6 is a cross-sectional view showing the vicinity of the liquidimmersion member according to a fourth embodiment.

FIG. 7 is a cross-sectional view showing the vicinity of the liquidimmersion member according to a fifth embodiment.

FIG. 8 is a cross-sectional view showing the vicinity of the liquidimmersion member according to a sixth embodiment.

FIG. 9 is a cross-sectional view showing the vicinity of the liquidimmersion member according to a seventh embodiment.

FIG. 10 is a flowchart illustrating an example of the processes ofmanufacturing microdevices.

DESCRIPTION OF EMBODIMENTS

Hereinafter, embodiments of the present invention will be described withreference to the drawings. However, the present invention is not limitedto these embodiments. In the following description, an XYZ orthogonalcoordinate system is set, and the positional relationship betweenrespective constituent elements will be described with reference to theXYZ orthogonal coordinate system. A predetermined direction within ahorizontal plane is defined as the X-axis direction, a directionorthogonal to the X-axis direction is defined as the Y-axis direction,and a direction (that is, a vertical direction) orthogonal to the X andY-axis directions is defined as the Z-axis direction. Moreover, thedirections of rotation (inclination) about the X, Y, and Z axes aredefined as the θX, θY, and θZ directions.

First Embodiment

The first embodiment will be described. FIG. 1 is a schematicconfiguration view showing an example of an exposure apparatus EXaccording to the first embodiment. The exposure apparatus EX of thepresent embodiment is a liquid immersion exposure apparatus that exposesa substrate P with exposure light EL via a liquid LQ. In the presentembodiment, a liquid immersion space LS is formed so that at least apart of the optical path of the exposure light EL is filled with theliquid LQ. The liquid immersion space LS is a portion (space or region)filled with the liquid LQ. The substrate P is exposed with the exposurelight EL via the liquid LQ in the liquid immersion space LS. In thepresent embodiment, water (pure water) is used as the liquid LQ.

In FIG. 1, the exposure apparatus EX includes a mask stage 1 configuredto be movable while holding a mask M, a substrate stage 2 configured tobe movable while holding the substrate P, an interferometer system 3that optically measures the positions of the mask stage 1 and thesubstrate stage 2, an illumination system IL that illuminates the mask Mwith the exposure light EL, a projection optical system PL that projectsthe image of the pattern on the mask M illuminated with the exposurelight EL onto the substrate P, a liquid immersion member 4 capable offorming the liquid immersion space LS so that at least a part of theoptical path of the exposure light EL is filled with the liquid LQ, achamber device 5 that accommodates at least the projection opticalsystem PL and the substrate stage 2, a body 6 that supports at least theprojection optical system PL, and a control device 7 that controls theoverall operation of the exposure apparatus EX.

The mask M includes a reticle on which a device pattern projected ontothe substrate P is formed. The mask M includes a transmissive mask whichincludes a transparent plate such as, for example, a glass plate, and apattern formed on the transparent plate using a light shielding materialsuch as chromium. A reflective mask may be used as the mask M.

The substrate P is a substrate used for manufacturing devices. Thesubstrate P includes a base such as, for example, a semiconductor wafer,and a multi-layer film formed on the base. The multi-layer film is afilm in which a plurality of films including at least a photosensitivefilm is laminated. The photosensitive film is a film formed of aphotosensitive material. Moreover, the multi-layer film may include ananti-reflection film and a protective film (top-coat film) forprotecting the photosensitive film, for example.

The chamber device 5 includes a chamber member 5A that forms asubstantially closed inner space 8 and an environment control device 5Bthat controls the environment (temperature, humidity, cleanness,pressure, and the like) of the inner space 8. The substrate stage 2moves inside the inner space 8. The control device 7 controls theenvironment of a space (the inner space 8), in which exposure of atleast the substrate P held on the substrate stage 2 is performed, usingthe environment control device 5A.

In the present embodiment, the body 6 is disposed in the inner space 8.The body 6 includes a first column 9 formed on a supporting surface FLand a second column 10 formed on the first column 9. The first column 9includes a first supporting member 11 and a first surface plate 13 thatis supported on the first supporting member 11 with an anti-vibrationdevice 12 disposed therebetween. The second column 10 includes a secondsupporting member 14 that is provided on the first surface plate 13 anda second surface plate 16 that is supported on the second supportingmember 14 with an anti-vibration device 15 disposed therebetween.Moreover, in the present embodiment, a third surface plate 18 isdisposed on the supporting surface FL with an anti-vibration device 17.

The illumination system IL irradiates a predetermined illuminationregion IR with the exposure light EL. The illumination region IRincludes positions which can be irradiated with the exposure light ELemitted from the illumination system IL. The illumination system ILilluminates at least a part of the mask M disposed in the illuminationregion IR with the exposure light EL having a uniform illuminancedistribution. As the exposure light EL emitted from the illuminationsystem IL, deep ultraviolet light (DUV light) such as emission lines (g,h, and i-rays) emitted from a mercury lamp or a KrF excimer laser beam(wavelength: 248 nm), vacuum ultraviolet light (VUV light) such as anArF excimer laser beam (wavelength: 193 nm) or an F₂ laser beam(wavelength: 157 nm), and the like are used, for example. In the presentembodiment, the ArF excimer laser beam, which is ultraviolet light(vacuum ultraviolet light), is used as the exposure light EL.

The mask stage 1 includes a mask holder 19 that releasably holds themask M, and is movable on a guide surface 16G of the second surfaceplate 16 in a state of holding the mask M. The mask stage 1 is movablerelative to the illumination region IR while holding the mask M by theoperation of a driving system 20. The driving system 20 includes aplanar motor which includes a movable member 20A disposed on the maskstage 1 and a stationary member 20B disposed on the second surface plate16. A planar motor capable of moving the mask stage 1 is disclosed inthe specification of U.S. Pat. No. 6,452,292, for example. The maskstage 1 is movable in the six directions of the X, Y, and Z-axisdirections and the θX, θY, and θZ directions by the operation of thedriving system 20.

The projection optical system PL irradiates a predetermined projectionregion PR with the exposure light EL. The projection optical system PLprojects the image of the pattern on the mask M onto at least a part ofthe substrate P disposed in the projection region PR at a predeterminedprojection magnification. The projection optical system PL of thepresent embodiment is a reduction system with a projectionmagnification, for example, of ¼, ⅕, ⅛, or the like. The projectionoptical system PL may be either a unity-magnification system or amagnification system. In the present embodiment, the optical axis AX ofthe projection optical system PL is parallel to the Z axis. Moreover,the projection optical system PL may be any one of a refracting systemwhich does not include a reflective optical element, a reflecting systemwhich does not include a refractive optical element, and a catadioptricsystem which includes a reflective optical element and a refractiveoptical element. In addition, the projection system PL may form eitheran inverted image or an upright image.

A plurality of optical elements of the projection optical system PL isheld on a holding member (lens barrel) 21. The holding member 21includes a flange 21F. The projection optical system PL is supported onthe first surface plate 13 with the flange 21F disposed therebetween. Ananti-vibration device may be provided between the first surface plate 13and the holding member 21.

The projection optical system PL includes an emission surface 23 fromwhich the exposure light EL is emitted toward the image plane of theprojection optical system PL. The emission surface 23 is disposed on aterminating optical element 22 which is closest to the image plane ofthe projection optical system PL among the plurality of optical elementsof the projection optical system PL. The projection region PR includes aposition which can be irradiated with the exposure light EL emitted fromthe emission surface 23. In the present embodiment, the emission surface23 faces the −Z direction and is parallel to the XY plane. The emissionsurface 23 facing the −Z direction may be a convex surface and may be aconcave surface.

In the present embodiment, the optical axis (an optical axis near theimage plane of the projection optical system PL) AX of the terminatingoptical element 22 is approximately parallel to the Z axis. In addition,an optical axis defined by an optical element adjacent to theterminating optical element 22 may be regarded as the optical axis ofthe terminating optical element 22. Moreover, in the present embodiment,the image plane of the projection optical system PL is approximatelyparallel to the XY plane that includes the X and Y axes. Furthermore, inthe present embodiment, the image plane is approximately horizontal.However, the image plane may not be parallel to the XY plane and may bea curved surface.

The substrate stage 2 includes a substrate holder 24 that releasablyholds the substrate P, and is movable on a guide surface 18G of thethird surface plate 18. The substrate stage 2 is movable relative to theprojection region PR while holding the substrate P by the operation of adriving system 25. The driving system 25 includes a planar motor whichincludes a movable member 25A disposed on the substrate stage 2 and astationary member 25B disposed on the third surface plate 18. A planarmotor capable of moving the substrate stage 2 is disclosed in thespecification of U.S. Pat. No. 6,452,292, for example. The substratestage 2 is movable in the six directions of the X, Y, and Z-axisdirections and the θX, θY, and θZ directions by the operation of thedriving system 25.

The substrate stage 2 includes an upper surface 26 which is disposedaround the substrate holder 24 so as to face the emission surface 23. Inthe present embodiment, the substrate stage 2 includes a plate memberholder 27 that is disposed in at least a part of the circumference ofthe substrate holder 24 so as to releasably hold the lower surface of aplate member T, as disclosed in the specification and the like of USPatent Application Publication No. 2007/0177125. In the presentembodiment, the upper surface 26 of the substrate stage 2 includes theupper surface of the plate member T. The upper surface 26 is flat. Theplate member T may not be releasable from the substrate stage 2.

In the present embodiment, the substrate holder 24 is capable of holdingthe substrate P so that the surface of the substrate P is approximatelyparallel to the XY plane. The plate member holder 27 is capable ofholding the plate member T so that the upper surface 26 of the platemember T is approximately parallel to the XY plane.

The interferometer system 3 includes a first interferometer device 3Acapable of optically measuring the position of the mask stage 1 (themask M) within the XY plane and a second interferometer device 3Bcapable of optically measuring the position of the substrate stage 2(the substrate P) within the XY plane. When executing an exposureprocess on the substrate P or executing a predetermined measurementprocess, the control device 7 operates the driving systems 20 and 25based on the results of the measurement by the interferometer system 3to thereby control the positions of the mask stage 1 (the mask M) andthe substrate stage 2 (the substrate P).

The liquid immersion member 4 is disposed in at least a part of thecircumference of the optical path of the exposure light EL. In thepresent embodiment, at least a part of the liquid immersion member 4 isdisposed in at least a part of the circumference of the terminatingoptical element 22. In the present embodiment, the liquid immersionmember 4 is supported on a supporting mechanism 28. In the presentembodiment, the supporting mechanism 28 is supported on the firstsurface plate 13. In the present embodiment, the liquid immersion member4 is suspended on the first surface plate 13 with the supportingmechanism 28 disposed therebetween.

The exposure apparatus EX of the present embodiment is a scanningexposure apparatus (commonly called a scanning stepper) which projectsthe image of the pattern on the mask M onto the substrate P while movingthe mask M and the substrate P in a predetermined scanning direction ina synchronized manner. When exposing the substrate P, the control device7 controls the mask stage 1 and the substrate stage 2 so as to move themask M and the substrate P in a predetermined scanning direction withinthe XY plane crossing the optical axis AX (the optical path of theexposure light EL). In the present embodiment, the scanning direction(synchronized moving direction) of the substrate P is the Y-axisdirection, and the scanning direction (synchronized moving direction) ofthe mask M is also the Y-axis direction. The control device 7 irradiatesthe substrate P with the exposure light EL via the projection opticalsystem PL and the liquid LQ in the liquid immersion space LS on thesubstrate P while moving the substrate P in the Y-axis directionrelative to the projection region PR of the projection optical system PLand moving the mask M in the Y-axis direction relative to theillumination region IR of the illumination system IL in synchronizationwith the movement of the substrate P in the Y-axis direction. In thisway, the image of the pattern on the mask M is projected onto thesubstrate P, and the substrate P is exposed with the exposure light EL.

Next, the liquid immersion member 4 will be described with reference toFIGS. 2 and 3. FIG. 2 is a side cross-sectional view showing thevicinity of the liquid immersion member 4, and FIG. 3 is an enlargedview of a part of FIG. 2.

In the present embodiment, the liquid immersion member 4 is an annularmember. At least a part of the liquid immersion member 4 is disposedaround a part of the optical path of the exposure light EL and theterminating optical element 22. In the present embodiment, the outershape of the liquid immersion member 4 within the XY plane is circular.The outer shape of the liquid immersion member 4 may be other shapes(for example, a rectangular shape).

The liquid immersion member 4 includes a lower surface 30 which isconfigured to face the surface (upper surface) of an object disposed ata position facing the emission surface 23. The liquid immersion member 4forms the liquid immersion space LS so that an optical path K of theexposure light EL between the emission surface 23 and an object disposedat the position facing the emission surface 23 is filled with the liquidLQ. The liquid LQ is held between the surface (upper surface) of theobject facing the lower surface 30 of the liquid immersion member 4 andat least a part of the lower surface 30 of the liquid immersion member4, and a part of the liquid immersion space LS is formed between thesurface of the object and the lower surface 30 of the liquid immersionmember 4. Moreover, in the present embodiment, a part of the liquidimmersion space LS is formed between the surface of the object and theterminating optical element 22, and between the terminating opticalelement 22 and the liquid immersion member 4. That is, in the presentembodiment, the liquid LQ in the liquid immersion space LS includes theliquid LQ held between the liquid immersion member 4 and the object, theliquid LQ held between the terminating optical element 22 and theobject, and the liquid LQ held between the liquid immersion member 4 andthe terminating optical element 22.

In the present embodiment, an object that is movable to the positionfacing the emission surface 23 includes at least one of the substratestage 2 (the plate member T) and the substrate P held on the substratestage 2. During exposure of the substrate P, the liquid immersion member4 forms the liquid immersion space LS so that the optical path K of theexposure light EL is filled with the liquid LQ.

Hereinafter, for the sake of simplicity, a case where the substrate P isdisposed at the position facing the emission surface 23 and the lowersurface 30, and the liquid LQ is held between the liquid immersionmember 4 and the substrate P, whereby the liquid immersion space LS isformed will be described as an example. In addition, the liquidimmersion space LS may be formed between the terminating optical element22 and the liquid immersion member 4 and other members (the plate memberT of the substrate stage 2, or the like).

In the present embodiment, the liquid immersion space LS is formed sothat a partial region of the surface of the substrate P including theprojection region PR is covered with the liquid LQ when the substrate Pis irradiated with the exposure light EL. The exposure apparatus EX ofthe present embodiment employs a local liquid immersion method.

In the present embodiment, a gas-liquid interface (meniscus) of theliquid LQ in the liquid immersion space LS includes a first interfaceLG1 disposed between the lower surface 30 of the liquid immersion member4 and the surface of the substrate P and a second interface LG2 disposedbetween a side surface 31 of the projection optical system PL differentfrom the emission surface 23 and an inner surface 32 of the liquidimmersion member 4 different from the lower surface 30.

The lower surface 30 of the liquid immersion member 4 is disposed in atleast a part of the circumference of the optical path K of the exposurelight EL emitted from the emission surface 23 of the projection opticalsystem PL. The lower surface 30 is configured to face the surface of thesubstrate P disposed at the position which can be irradiated with theexposure light EL emitted from the emission surface 23. The emissionsurface 23 and the lower surface 30 are configured to face the surfaceof the substrate P disposed below the liquid immersion member 4. Theemission surface 23 and the lower surface 30 face the surface of thesubstrate P during at least a part of the exposure period for thesubstrate P.

The side surface 31 of the projection optical system PL includes anouter side surface 31A of the terminating optical element 22 disposedaround the emission surface 23 and a lower surface 31B that is disposedaround the outer side surface 31A and faces downward. The outer sidesurface 31A and the lower surface 31B are surfaces through which theexposure light EL does not pass.

The inner surface 32 of the liquid immersion member 4 faces at least apart of the side surface 31 of the projection optical system PL at anupper side than the emission surface 23. The inner surface 32 of theliquid immersion member 4 includes an inner side surface 32A of theliquid immersion member 4 facing the outer side surface 31A and an uppersurface 32B of the liquid immersion member 4 facing the lower surface31B. In the present embodiment, the interface LG2 is disposed betweenthe outer side surface 31A and the inner side surface 32A.

In the present embodiment, the liquid immersion member 4 includes aplate portion 41 which is disposed so that at least a part thereof facesthe emission surface 23 and a body portion 42 in which at least a partthereof is disposed around the terminating optical element 22. The lowersurface 30 is disposed on the plate portion 41 and the body portion 42.The inner side surface 32A and the upper surface 32B are disposed on thebody portion 42. The inner side surface 32A faces the outer side surface31A via a gap. The upper surface 32B faces the lower surface 31B via agap.

In the present embodiment, the upper surface 32B faces at least a partof the surface of the terminating optical element 22. In the presentembodiment, the terminating optical element 22 includes a flange portion22F disposed around the outer side surface 31A, and the lower surface31B includes the lower surface of the flange portion 22F. In addition,the upper surface 32B may face the surface (lower surface) of theholding member 21 of the projection optical system PL, and may face boththe surface of the terminating optical element 22 and the surface of theholding member 21. Moreover, at least a part of the inner side surface32A may face a part of the holding member 21, and may face theterminating optical element 22 and the holding member 21.

Moreover, the plate portion 41 of the liquid immersion member 4 isdisposed in at least a part of the circumference of the optical path Kof the exposure light EL, and includes an upper surface 33 in which atleast a part thereof faces the emission surface 23. The upper surface 33faces in the reverse direction of the lower surface 30.

The liquid immersion member 4 (the plate portion 41) includes an opening34 that the exposure light EL emitted from the emission surface 23 canpass. The lower surface 30 and the upper surface 33 are disposed aroundthe opening 34. During exposure of the substrate P, the exposure lightEL emitted from the emission surface 23 is irradiated on the surface ofthe substrate P through the opening 34. In the present embodiment, theopening 34 is long in the X-axis direction crossing the scanningdirection (Y-axis direction) of the substrate P.

In the present embodiment, the liquid immersion member 4 includes aliquid supply port 35 for supplying the liquid LQ in order to fill theoptical path K of the exposure light EL with the liquid LQ, a gas supplyport 36 for supplying a gas GD including a material capable of changingthe specific resistance of the liquid LQ to at least a part of a spaceS1 around the liquid immersion space LS formed by the liquid LQ, and agas supply port 37 disposed at a position different from the gas supplyport 36 so as to supply a gas GD including a material capable ofchanging the specific resistance of the liquid LQ to at least a part ofa space S2 around the liquid immersion space LS.

The gas supply port 36 supplies the gas GD to at least a part of a spacebetween the liquid immersion member 4 and the substrate P. The gassupply port 36 supplies the gas GD to at least a part of the space S1around the interface LG1, located between the lower surface 30 of theliquid immersion member 4 and the surface of the substrate P.

The gas supply port 37 supplies the gas GD to at least a part of a spacebetween the projection optical system PL and the liquid immersion member4. The gas supply port 37 supplies the gas GD to at least a part of thespace S2 around the interface LG2, located between the side surface 31of the projection optical system PL and the inner surface 32 of theliquid immersion member 4. In the present embodiment, the gas GDsupplied from the gas supply ports 36 and 37 includes a larger amount ofthe material that changes (decreases) the specific resistance of theliquid LQ than the gas in the inner space 8 controlled by the chamberdevice 5 (the environment control device 5B). That is, in the presentembodiment, by supplying the gas GD from the gas supply ports 36 and 37,the gas spaces S1 and S2 in which the concentration (proportion) of thematerial that changes the specific resistance of the liquid LQ is higherthan that of the inner space 8 are formed in at least a part of thecircumference of the liquid immersion space LS.

In the present embodiment, the material capable of changing the specificresistance of the liquid LQ is carbon dioxide. The gas supply ports 36and 37 supply the gas (carbonic acid gas) GD including carbon dioxide.

Carbon dioxide is soluble in the liquid LQ supplied from the liquidsupply port 35. Moreover, carbon dioxide can decrease the specificresistance of the liquid LQ.

At least some of the gas GD supplied from the gas supply port 36 to thespace S1 between the lower surface 30 of the liquid immersion member 4and the surface of the substrate P comes into contact with the interfaceLG1. The gas GD including carbon dioxide supplied so as to come intocontact with the interface LG1 is dissolved in the liquid LQ, wherebythe specific resistance of the liquid LQ is decreased.

That is, in the present embodiment, the gas GD including carbon dioxidesupplied to the space S1 around the interface LG1 of the liquidimmersion space LS is mixed into and dissolved in some of the liquid LQin the vicinity of the interface LG1. In this way, some of the liquid LQ(pure water) which is supplied from the liquid supply port 35 andpresent in the vicinity of the interface LG1 is changed into carbonatedwater. Thus, the specific resistance of the liquid LQ in the vicinity ofthe interface LG1 decreases.

As above, in the present embodiment, the gas GD supplied to the space S1is dissolved in some of the liquid LQ in the liquid immersion space LS,located between the liquid immersion member 4 and the substrate P,whereby the specific resistance of some of the liquid LQ is decreased.Thus, charging of the liquid LQ in the vicinity of the interface LG1 issuppressed.

Similarly, at least some of the gas GD supplied from the gas supply port37 to the space between the side surface 31 of the projection opticalsystem PL and the inner surface 32 of the liquid immersion member 4comes into contact with the interface LG2. The gas GD including carbondioxide supplied so as to come into contact with the interface LG2 isdissolved in the liquid LQ in the vicinity of the interface LG2, wherebythe specific resistance of the liquid LQ in the vicinity of theinterface LG2 is decreased. Thus, the specific resistance of the liquidLQ in the vicinity of the interface LG2 decreases.

In addition, the gas GD may be composed only of carbon dioxide(conductive adhesive agent), and may be a mixed gas of carbon dioxideand other gases (clean air or the like), for example.

The material capable of changing the specific resistance of the liquidLQ may not be carbon dioxide but may be ozone or hydrogen, for example.Such materials can decrease the specific resistance of the liquid LQ bybeing mixed into the liquid LQ. Moreover, the gas GD may include two ormore kinds of materials capable of changing the specific resistance ofthe liquid LQ, and may include two or more kinds of optional materialsselected from carbon dioxide, ozone, and hydrogen described above, forexample.

Moreover, in the present embodiment, the liquid immersion member 4includes a gas recovery port 38 for recovering at least some of the gasGD and a gas recovery port 39 disposed at a position different from thegas recovery port 38 so as to recover at least some of the gas GD. Thegas recovery port 38 recovers at least some of the gas GD in the spaceS1 around the interface LG1, located between the lower surface 30 of theliquid immersion member 4 and the surface of the substrate P. The gasrecovery port 39 recovers at least some of the gas GD in the space S2around the interface LG2, located between the side surface 31 of theprojection optical system PL and the inner surface 32 of the liquidimmersion member 4.

Moreover, in the present embodiment, the liquid immersion member 4includes a liquid recovery port 40 for recovering at least some of theliquid LQ.

In the present embodiment, the liquid supply port 35 supplies the liquidLQ to the space between the liquid immersion member 4 and theterminating optical element 22. In the present embodiment, the liquidsupply port 35 is disposed on the inner side surface 32A. In the presentembodiment, the liquid supply port 35 is disposed on a predeterminedportion of the liquid immersion member 4 so as to face the optical pathK. In the present embodiment, the liquid supply port 35 supplies theliquid LQ to the space between the emission surface 23 and the uppersurface 33.

In addition, the liquid supply port 35 may be disposed on the inner sidesurface 32A so as to face the outer side surface 31A and may supply theliquid LQ to the space between the outer side surface 31A and the innerside surface 32A.

In the present embodiment, the liquid supply port 35 is disposed on eachof the +Y and −Y sides in relation to the opening 34 (the optical path Kof the exposure light EL). In addition, the liquid supply port 35 may bedisposed on each of the +X and −X sides in relation to the opening 34(the optical path K of the exposure light EL). Moreover, the number ofliquid supply ports 35 is not limited to two. The liquid supply port 35may be disposed at three or more positions around the optical path K ofthe exposure light EL.

The liquid LQ from the liquid supply port 35 is supplied to the opticalpath K of the exposure light EL. In this way, the optical path K of theexposure light EL is filled with the liquid LQ.

In the present embodiment, the liquid recovery port 40 is disposed on atleast a part of the lower surface 30. In the present embodiment, thesurface of the substrate P disposed below the liquid immersion member 4is configured to face the liquid recovery port 40.

In the present embodiment, the liquid recovery port 40 is disposed onthe lower surface 30 in at least a part of the circumference of theoptical path K (the optical axis AX). The liquid recovery port 40 iscapable of recovering the liquid LQ on the substrate P (object) disposedat the position facing the lower surface 30. In the present embodiment,the shape of the liquid recovery port 40 within the XY plane isring-shaped (circular and annular).

In addition, the shape of the liquid recovery port 40 within the XYplane may be rectangular and annular. Moreover, the liquid recovery port40 may be disposed in at least a part of the circumference of theoptical path K. For example, the liquid recovery port 40 may be disposedon only one side (+Y side) and the other side (−Y side) in the scanningdirection of the substrate P in relation to the optical path K (opening34), and a plurality of liquid recovery ports 40 may be disposed on thelower surface 30 around the optical path K at predetermined intervals.

In the present embodiment, a porous member 41 is disposed in the liquidrecovery port 40. The porous member 41 is a plate-shaped memberincluding a plurality of openings or pores. In addition, the porousmember 41 may be a mesh filter which is a porous member 41 in which anumber of small openings or pores are formed in a network shape. Theliquid recovery port 40 recovers the liquid LQ on the substrate Pthrough the openings or pores of the porous member 41.

In the present embodiment, the operation of recovering the liquid LQ bythe liquid recovery port 40 is executed concurrently with the operationof supplying the liquid LQ by the liquid supply port 35 during at leasta part of the exposure period for the substrate P. During at least apart of the exposure period for the substrate P, at least some of theliquid LQ supplied from the liquid supply port 35 to the space betweenthe emission surface 23 and the upper surface 33 is supplied to thespace between the lower surface 30 and the surface of the substrate Pthrough the opening 34, whereby the optical path K of the exposure lightEL is filled with the liquid LQ. Moreover, some of the liquid LQ is heldbetween the lower surface 30 and the surface of the substrate P. Sincethe operation of recovering the liquid LQ by the liquid recovery port 40is executed concurrently with the operation of supplying the liquid LQby the liquid supply port 35, the size (volume) of the liquid immersionspace LS formed between the liquid immersion member 4 and the substrateP is determined. The substrate P is exposed with the exposure light ELfrom the emission surface 23 via the liquid LQ between the emissionsurface 23 and the surface of the substrate P.

The gas supply port 36 is disposed on a predetermined portion of theliquid immersion member 4 so as to face the space S1. In the presentembodiment, the gas supply port 36 is disposed on at least a part of thelower surface 30.

The gas supply port 36 is disposed on the outer side of the liquidrecovery port 40 in the radiation direction in relation to the opticalaxis AX. The gas supply port 36 is disposed on at least a part of thelower surface 30 around the optical path K (the optical axis AX). In thepresent embodiment, the gas supply port 36 is disposed at a positionwhere it does not come into contact with the liquid LQ. That is, the gassupply port 36 is disposed on the outer side of the interface LG1 in theradiation direction in relation to the optical axis AX.

In the present embodiment, the gas supply port 36 supplies the gas GDtoward the surface of the substrate P facing the gas supply port 36. Inaddition, the gas supply port 36 may supply the gas GD toward the innerside (toward the interface LG1) in the radiation direction in relationto the optical axis AX.

In the present embodiment, the gas supply port 36 is disposed in atleast a part of the circumference of the optical path K (the opticalaxis AX). In the present embodiment, the shape of the gas supply port 36within the XY plane is ring-shaped (circular and annular). In thepresent embodiment, the gas supply port 36 is a slit opening that isformed so as to surround the optical path K of the exposure light EL. Inaddition, the shape of the gas supply port 36 within the XY plane may berectangular or annular.

In the present embodiment, a concave portion 42 is formed on at least apart of the lower surface 30. The concave portion 42 is recessed so asto be away from the surface of the substrate P facing the lower surface30. In the present embodiment, the gas supply port 36 is disposed on theinner surface of a concave portion that defines the concave portion 42.

In the present embodiment, the shape of the concave portion 42 withinthe XY plane is ring-shaped (circular and annular). In addition, theshape of the concave portion 42 within the XY plane may be rectangularor annular.

The gas supply port 36 may be disposed in at least a part of thecircumference of the optical path K (the optical axis AX). For example,a plurality of gas supply ports 36 may be disposed on the lower surface30 around the optical path K at predetermined intervals. In this case, aplurality of concave portions 42 may be disposed on the lower surface 30at predetermined intervals, and at least one gas supply port 36 may bedisposed in a part or all of the plurality of concave portions 42.

The plurality of gas supply ports 36 may be disposed to be separated inthe radiation direction in relation to the optical axis AX. For example,the gas supply port 36 may include a first annular gas supply portdisposed around the optical path K and a second gas supply port disposedon the outer side of the first gas supply port so as to be approximatelyconcentric to the first gas supply port. In this case, both the firstand second gas supply ports may be disposed on the inner surface of theconcave portion 42, and any one of the first and second gas supply portsmay be disposed on the lower surface 30 on the outer side of the concaveportion 42, and the other may be disposed on the inner surface of theconcave portion 42.

The concave portion 42 may not be provided, and the gas supply port 36may be disposed on the lower surface 30.

The gas recovery port 38 is disposed in the liquid immersion member 4 soas to face the space S1. In the present embodiment, the gas recoveryport 38 is disposed on at least a part of the lower surface 30.

In the present embodiment, the gas recovery port 38 is disposed on theouter side of the gas supply port 36 in the radiation direction inrelation to the optical axis AX. The gas recovery port 38 is disposed onat least a part of the lower surface 30 around the gas supply port 36.The gas recovery port 38 is capable of recovering at least a part of thegas GD in the space S1 around the interface LG1.

In the present embodiment, the shape of the gas recovery port 38 withinthe XY plane is ring-shaped (circular and annular). In the presentembodiment, the gas recovery port 38 is a slit opening that is formed soas to surround the optical path K of the exposure light EL. In addition,the shape of the gas recovery port 38 within the XY plane may berectangular or annular.

In the present embodiment, a concave portion 43 is formed on at least apart of the lower surface 30. The concave portion 43 is recessed so asto be away from the surface of the substrate P facing the lower surface30. The concave portion 43 is disposed around the optical path K (theoptical axis AX). The concave portion 43 is disposed on the outer sideof the concave portion 42 in the radiation direction in relation to theoptical axis AX. In the present embodiment, the gas recovery port 38 isdisposed on the inner surface of the concave portion 43 that defines theconcave portion 43.

In the present embodiment, the shape of the concave portion 43 withinthe XY plane is ring-shaped (circular and annular). In addition, theshape of the concave portion 43 within the XY plane may be rectangularand annular.

The gas recovery port 38 may be disposed in at least a part of thecircumference of the gas supply port 36. For example, a plurality of gasrecovery ports 38 may be disposed on the lower surface 30 around theoptical path K (the optical axis AX) at predetermined intervals. In thiscase, a plurality of concave portions 43 may be disposed on the lowersurface 30 around the optical path K at predetermined intervals, and atleast one gas recovery port 38 may be disposed in each of the pluralityof concave portions 43. Moreover, the plurality of gas recovery ports 38may be disposed so as to be separated in the radiation direction inrelation to the optical axis AX. In this case, both a gas recovery portlocated closest to the optical path K (the optical axis AX) and a gasrecovery port located farther from the optical axis AX than the firstgas recovery port may be disposed on the inner surface of the concaveportion 43, and any one of them may be disposed on the inner surface ofthe concave portion 43.

In the present embodiment, a humidifying system 44 is provided so as tomake the humidity of the space S1 supplied with the gas GD from the gassupply port 36 higher than the humidity of the inner space 8 controlledby the chamber device 5 (the environment control device 5B). Thehumidifying system 44 humidifies the gas GD with the steam GW of theliquid LQ.

In the present embodiment, the humidifying system 44 includes an airsupply port 45 for supplying the steam GW of the liquid LQ to the spaceS1. In the present embodiment, the air supply port 45 is disposed on thelower surface 30 of the liquid immersion member 4 so as to face thespace S1.

In the present embodiment, the inner space 8 of the chamber device 5 isfilled with clean air, and the air supply port 45 supplies airhumidified by water vapor to the space S1.

In the present embodiment, the air supply port 45 is disposed in thevicinity of the gas supply port 36. In the present embodiment, the airsupply port 45 is disposed on the inner surface of the concave portion42.

In the present embodiment, the shape of the air supply port 45 withinthe XY plane is ring-shaped (circular and annular). In the presentembodiment, the air supply port 45 is a slit opening that is formed soas to surround the optical path K of the exposure light EL. In addition,the shape of the air supply port 45 within the XY plane may berectangular and annular.

A plurality of air supply ports 45 may be disposed so as to be separatedin the radiation direction in relation to the optical axis AX. Moreover,the air supply port 45 may be disposed in at least a part of thecircumference of the optical path K. For example, a plurality of airsupply ports 45 may be disposed on the lower surface 30 around theoptical path K at predetermined intervals. Moreover, the air supply port45 may be disposed on the lower surface 30 on the outer side of theconcave portion 42. Furthermore, a part of the plurality of air supplyports 45 may be disposed on the concave portion 42, and the remainingair supply ports may be disposed on the lower surface 30 on the outerside of the concave portion 42.

The gas supply port 37 is disposed on a predetermined portion of theliquid immersion member 4 so as to face the space S2. In the presentembodiment, the gas supply port 37 is disposed on at least a part of theinner side surface 32A.

The gas supply port 37 is disposed above the emission surface 23. Thegas supply port 37 is disposed at a position where it does not come intocontact with the liquid LQ. That is, the gas supply port 37 is disposedabove the interface LG2.

In the present embodiment, the gas supply port 37 supplies the gas GDtoward the outer side surface 31A of the terminating optical element 22facing the gas supply port 37. In addition, the gas supply port 37 maysupply the gas GD toward the lower side (toward the interface LG2).

In the present embodiment, the gas supply port 37 is annular. In thepresent embodiment, the gas supply port 37 is a slit opening that isformed so as to surround the outer side surface 31A.

The gas supply port 37 may be disposed around a part of the optical axisAX. For example, a plurality of gas supply ports 37 may be disposed onthe inner side surface 32A around the optical axis AX at predeterminedintervals.

The gas recovery port 39 is disposed in the liquid immersion member 4 soas to face the space S2. In the present embodiment, the gas recoveryport 39 is disposed on at least a part of the inner side surface 32A.

The gas recovery port 39 is disposed above the gas supply port 37. Inthe present embodiment, the gas recovery port 39 is annular. In thepresent embodiment, the gas recovery port 39 is a slit opening that isformed so as to surround the outer side surface 31A.

The gas recovery port 39 may be disposed around a part of the opticalpath K. For example, a plurality of gas recovery ports 39 may bedisposed on the inner side surface 32A around the optical axis AX atpredetermined intervals.

The gas supply port 37 and the gas recovery port 39 may be disposed onthe upper surface 32B. Moreover, the gas supply port 37 may be disposedon the inner side surface 32A, and the gas recovery port 39 may bedisposed on the upper surface 32B.

As shown in FIG. 2, the liquid supply port 35 is connected to a liquidsupply apparatus 46 through a supply flow channel. The supply flowchannel includes an inner flow channel of the liquid immersion member 4and a flow channel of a supply pipe that connects the inner flow channeland the liquid supply apparatus 46. The liquid supply apparatus 46supplies clean and temperature-adjusted liquid LQ to the liquid supplyport 35.

The liquid recovery port 40 is connected to a liquid recovery apparatus47 through a recovery flow channel. In the present embodiment, therecovery flow channel includes an inner flow channel of the liquidimmersion member 4 and a flow channel of a recovery pipe that connectsthe inner flow channel and the liquid recovery apparatus 47. The liquidrecovery apparatus 47 includes a vacuum system (a valve or the like thatcontrols the connection state between a vacuum source and the liquidrecovery port 40) and is capable of sucking and recovering the liquid LQfrom the liquid recovery port 40.

In the present embodiment, the control device 7 is capable ofcontrolling the liquid recovery apparatus 47 to control a pressuredifference between the upper surface side and the lower surface side ofthe porous member 41 so that only the liquid LQ passes from the lowersurface-side space of the porous member 41 (the space between the lowersurface of the porous member 41 and the surface of the substrate P)toward the upper surface-side space (the recovery flow channel). In thepresent embodiment, the lower surface-side space is open to theatmosphere and the pressure thereof is controlled by the chamber device5. The control device 7 controls the liquid recovery apparatus 47 so asto adjust the pressure of the upper surface side in accordance with thepressure of the lower surface side so that only the liquid LQ passesfrom the lower surface side of the porous member 41 toward the uppersurface side. That is, the control device 7 adjusts the pressure of theupper surface-side space so that gas does not pass through the openingsor pores of the porous member 41. A technique of adjusting the pressuredifference between one side and the other side of the porous member 41so that only the liquid LQ passes from one side of the porous member 41toward the other side is disclosed in the specification and the like ofU.S. Pat. No. 7,292,313, for example.

In the present embodiment, “atmosphere” is gas surrounding the liquidimmersion member 4. In the present embodiment, the gas surrounding theliquid immersion member 4 is the gas in the inner space 8 which isformed by the chamber device 5. In the present embodiment, the chamberdevice 5 fills the inner space 8 with clean air using the environmentcontrol device 5B. Moreover, the chamber device 5 adjusts the pressureof the inner space 8 to approximately atmospheric pressure using theenvironment control device 5B. Naturally, the pressure of the innerspace 8 may be set to be higher than the atmospheric pressure.

In the present embodiment, the space between the side surface 31 of theprojection optical system PL and the inner surface 32 of the liquidimmersion member 4 is open to the atmosphere. Moreover, the spacebetween the lower surface 30 of the liquid immersion member 4 and thesurface of the substrate P is also open to the atmosphere.

The gas supply port 36 is connected to a gas supply apparatus 48 througha gas supply flow channel. The gas supply flow channel includes an innerflow channel of the liquid immersion member 4 and a flow channel of agas supply pipe that connects the inner flow channel and the gas supplyapparatus 48. The gas supply apparatus 48 can supply clean andtemperature-adjusted gas GD to the gas supply port 36.

Similarly, the gas supply port 37 is connected to a gas supply apparatus49 through a gas supply flow channel.

The air supply port 45 is connected to a humidifying apparatus 50through a supply flow channel. The supply flow channel includes an innerflow channel of the liquid immersion member 4 and a flow channel of asupply pipe that connects the inner flow channel and the humidifyingapparatus 50. The humidifying apparatus 50 supplies the steam GW of theliquid LQ to the air supply port 45.

The gas recovery port 38 is connected to a gas recovery apparatus 51through a recovery flow channel. In the present embodiment, the recoveryflow channel includes an inner flow channel of the liquid immersionmember 4 and a flow channel of a recovery pipe that connects the innerflow channel and the gas recovery apparatus 51. The gas recoveryapparatus 51 includes a vacuum system and is capable of sucking andrecovering gas in the space S1 from the gas recovery port 38.

Similarly, the gas recovery port 39 is connected to a gas recoveryapparatus 52 through a recovery flow channel.

Next, a method of exposing the substrate P using the exposure apparatusEX having the configuration described above will be described.

First, the control device 7 causes the emission surface 23 of theprojection optical system PL and the lower surface 30 of the liquidimmersion member 4 to face the surface of the substrate P (or the uppersurface 26 of the substrate stage 2).

The control device 7 causes the liquid LQ to be delivered from theliquid supply apparatus 46 in a state where the emission surface 23 andthe lower surface 30 face the surface of the substrate P. Moreover, thecontrol device 7 operates the liquid recovery apparatus 47. The liquidLQ delivered from the liquid supply apparatus 46 is supplied to theliquid supply port 35. The liquid supply port 35 supplies the liquid LQto the space between the emission surface 23 and the upper surface 33 sothat the optical path K between the emission surface 23 and the surfaceof the substrate P is filled with the liquid LQ. The liquid LQ suppliedfrom the liquid supply port 35 to the space between the emission surface23 and the upper surface 33 is supplied to the optical path K of theexposure light EL emitted from the emission surface 23. In this way, theoptical path K of the exposure light EL is filled with the liquid LQ.

Moreover, at least some of the liquid LQ supplied from the liquid supplyport 35 is supplied to the space between the lower surface 30 and thesurface of the substrate P through the opening 34 and is held betweenthe lower surface 30 and the surface of the substrate P. In this way,the liquid immersion space LS is formed by the liquid LQ supplied fromthe liquid supply port 35 so that the optical path K of the exposurelight EL, located between the emission surface 23 and the substrate P isfilled with the liquid LQ.

At least some of the liquid LQ between the lower surface 30 and thesurface of the substrate P is recovered through the liquid recovery port40. The liquid LQ recovered from the liquid recovery port 40 isrecovered into the liquid recovery apparatus 47.

Moreover, the control device 7 causes the gas GD to be delivered fromthe gas supply apparatuses 48 and 49. Moreover, the control device 7operates the gas recovery apparatuses 51 and 52. Moreover, the controldevice 7 operates the humidifying apparatus 50.

The gas GD delivered from the gas supply apparatus 48 is supplied to atleast a part of the space S1 around the liquid immersion space LS of theliquid LQ formed on the substrate P through the gas supply port 36.Moreover, the steam GW delivered from the humidifying apparatus 50 issupplied to at least a part of the space S1 through the air supply port45. Furthermore, the gas GD delivered from the gas supply apparatus 49is supplied to at least a part of the space S2 around the liquidimmersion space LS through the gas supply port 37.

The control device 7 controls the liquid supply apparatus 46, the liquidrecovery apparatus 47, the gas supply apparatus 48, the humidifyingapparatus 50, the gas recovery apparatus 51, the gas supply apparatus49, and the gas recovery apparatus 52 so that the operation of supplyingthe liquid LQ by the liquid supply port 35, the operation of recoveringthe liquid LQ by the liquid recovery port 40, the operation of supplyingthe gas GD by the gas supply port 36, the operation of supplying thesteam GW by the air supply port 45, the operation of recovering the gasGD and the steam GW by the gas recovery port 38, the operation ofsupplying the gas GD by the gas supply port 37, and the operation ofrecovering the gas GD by the gas recovery port 39 are executedconcurrently. That is, the control device 7 supplies the gas GD and thesteam GW to the space S1 around the liquid immersion space LS andrecovers the gas GD and the steam GW in the space S1 in a state wherethe liquid immersion space LS is formed by the liquid LQ supplied fromthe liquid supply port 35. Moreover, the control device 7 supplies thegas GD to the space S2 around the liquid immersion space LS and recoversthe gas GD in the space S2 in a state where the liquid immersion spaceLS is formed.

The control device 7 starts the exposure of the substrate P in a statewhere the liquid immersion space LS is formed. The control device 7causes the exposure light EL to be emitted from the illumination systemIL so that the mask M is illuminated with the exposure light EL. Theexposure light EL from the mask M is emitted from the emission surface23 of the projection optical system PL. The control device 7 exposes thesubstrate P with the exposure light EL from the emission surface 23 viathe liquid LQ between the emission surface 23 and the surface of thesubstrate P. In this way, the image of the pattern on the mask M isprojected onto the substrate P, and the substrate P is exposed with theexposure light EL. During the exposure of the substrate P, the operationof supplying the liquid LQ by the liquid supply port 35, the operationof recovering the liquid LQ by the liquid recovery port 40, theoperation of supplying the gas GD by the gas supply port 36, theoperation of supplying the steam GW by the air supply port 45, theoperation of recovering the gas GD and the steam GW by the gas recoveryport 38, the operation of supplying the gas GD by the gas supply port37, and the operation of recovering the gas GD by the gas recovery port39 are executed concurrently.

Since the gas GD is supplied to the space S1, charging of the liquid LQin the vicinity of the interface LG1 is suppressed. Moreover, chargingof the liquid immersion member 4 contacting the liquid LQ, charging ofthe substrate P, and charging of the substrate stage 2 (the plate memberT) are suppressed.

In the present embodiment, since the concave portions 42 and 43 areprovided, it is possible to increase the size of the space S1 in whichthe gas GD is filled. Thus, the gas GD in the space S1 can be smoothlydissolved in the liquid LQ, and charging can be suppressed.

Moreover, since the gas GD is supplied to the space S2, charging of theliquid LQ in the vicinity of the interface LG2 is suppressed. Moreover,charging of the liquid immersion member 4 contacting the liquid LQ andcharging of the terminating optical element 22 are suppressed.

Furthermore, since the gas GD in the space S1 is recovered from the gasrecovery port 38, the gas GD is suppressed from flowing into a space(the atmosphere or the inner space 8) around the liquid immersion member4. Similarly, the gas recovery port 39 suppresses the gas GD in thespace S2 from flowing into the space around the liquid immersion member4.

Moreover, in the present embodiment, the steam GW is supplied to thespace S1 in which the gas GD is supplied. By causing the gas GD and theliquid LQ to contact each other in a state where the humidity of thespace S1 around the liquid immersion space LS is high, the gas GD (thematerial that changes the specific resistance of the liquid LQ) becomeseasily dissolved in the liquid LQ. Thus, by supplying the steam GW tothe space S1, dissolution of the gas GD in the liquid LQ is accelerated,and charging of the liquid LQ can be suppressed more effectively.

Moreover, by increasing the humidity of the space S1 around the liquidimmersion space LS, it is possible to suppress vaporization of theliquid LQ in the liquid immersion space LS. Thus, it is possible tosuppress the occurrence of a temperature change of the liquid LQ, theliquid immersion member 4, and the substrate stage 2 (the plate memberT) due to vaporization heat of the liquid LQ.

The gas supply apparatus 48 may supply a humidified gas GD to the gassupply port 36. That is, the gas supply apparatus 48 may include ahumidifying apparatus. In this case, the humidifying system 44 whichincludes the humidifying apparatus 50 and the air supply port 45 may notbe provided. Moreover, the gas supply apparatus 49 may supply thehumidified gas GD to the gas supply port 37.

In the present embodiment, the control device 7 may adjust at least oneof the supply amount per unit time of the gas GD supplied from the gassupply port 36 to the space S1 and the supply amount per unit time ofthe gas GD supplied from the gas supply port 37 to the space S2. Forexample, a sensor capable of detecting the charge quantity of the liquidLQ is provided, and the control device 7 adjusts the supply amount ofthe gas GD based on the results of the detection by the sensor. Forexample, the control device 7 can adjust the supply amount of the gas GDbased on the results of the detection by a capacitance sensor which isprovided on at least a part of the liquid immersion member 4 and iscapable of detecting the charge quantity of the liquid LQ. The specificresistance of the liquid LQ changes with the supply amount of the gasGD. For example, when the charge quantity of the liquid LQ is determinedto be large based on the detection results from the sensor, the controldevice 7 increases the supply amount of the gas GD. On the other hand,when the charge quantity of the liquid LQ is determined to be small, thecontrol device 7 decreases the supply amount of the gas GD. Moreover,the control device 7 may adjust at least one of the proportion(concentration) of the carbon dioxide included in the gas GD suppliedfrom the gas supply port 36 and the proportion (concentration) of thecarbon dioxide included in the gas GD supplied from the gas supply port37. In this case, adjustment can be performed based on the resultsobtained by the sensor described above. Moreover, the control device 7may adjust the amount (flow rate) per unit time of the steam GW suppliedfrom the air supply port 45 to the space S1. In this case, adjustmentcan be performed based on the results of the detection by the sensor.

When the liquid LQ supplied from the liquid supply port 35 is pure water(ultrapure water), the possibility of charging of the liquid LQincreases. Moreover, when the surface of a member contacting the liquidLQ such as the upper surface 26 of the substrate stage 2 (the platemember T) or the surface of the substrate P has insulating properties,the possibility of charging of the member increases. For example, whenthe upper surface 26 of the substrate stage 2 is formed of a liquidrepellent material (fluorinated material or the like) having insulatingproperties, the possibility of charging increases. Moreover, when thesurface of the substrate P is formed of an insulating top-coat film, thepossibility of charging increases. Moreover, the exposure apparatus EXof the present embodiment is a scanning exposure apparatus, in whichwhen the substrate P (the substrate stage 2) moves in a predetermineddirection within the XY plane in a state where the liquid immersionspace LS is formed, the possibility that at least one of the liquid LQand the member (the substrate P, the substrate stage 2, or the like)contacting the liquid LQ may be charged increases.

According to the present embodiment, since the gas GD including thematerial capable of changing the specific resistance of the liquid LQ issupplied t the spaces S1 and S2 around the liquid immersion space LS, itis possible to suppress charging of the liquid LQ and the membercontacting the liquid LQ. That is, since the supplied gas GD changes theliquid LQ in the vicinity of the interfaces LG1 and LG2 into carbonatedwater, so that the specific resistance of the liquid LQ is changed, itis possible to suppress charging of the liquid LQ in the vicinity of theinterfaces LG1 and LG2. In particular, the present embodiment iseffective when the liquid LQ in the vicinity of the interfaces LG1 andLG2 is likely to be charged.

In the present embodiment, the space S1 around the interface LG1 isfilled with the gas GD, and the space S2 around the interface LG2 isfilled with the gas GD. Thus, the spaces S1 and S2 filled with the gasGD suppress the liquid LQ in the liquid immersion space LS from cominginto contact with the gas (air in the present embodiment) in the innerspace 8 controlled by the chamber device 5.

In the present embodiment, since the gas GD including the materialcapable of changing the specific resistance of the liquid LQ is suppliedto the spaces S1 and S2 around the liquid immersion space LS formed bythe liquid LQ which is supplied from the liquid supply port 35, it ispossible to suppress charging of the liquid LQ in the periphery of theliquid immersion space LS and the member contacting the liquid LQ whilesuppressing a change in the properties of the liquid LQ in the opticalpath K of the exposure light EL. Therefore, it is possible to expose thesubstrate P satisfactorily.

As described above, according to the present embodiment, it is possibleto suppress charging of the liquid LQ in the liquid immersion space LSand charging of the member contacting the liquid LQ. Thus, it ispossible to suppress the occurrence of exposure defects and to suppressthe occurrence of defective devices.

For example, when at least one of the liquid LQ and the member ischarged, there is a possibility that foreign materials (particles) areadsorbed to the liquid LQ or the member, and exposure defects occur.Examples of foreign materials include foreign materials generated fromthe substrate P (flakes of part of a photosensitive film, flakes of partof an top-coat film, flakes of part of an anti-reflection film, or thelike), or foreign materials floating around the substrate stage 2.

According to the present embodiment, since charging of the liquid LQ andthe member contacting the liquid LQ is suppressed, it is possible tosuppress foreign materials from being adsorbed to the liquid LQ and themember. Thus, it is possible to suppress the occurrence of exposuredefects.

Second Embodiment

Next, the second embodiment will be described. In the followingdescription, constituent elements which are the same as or similar tothose of the above embodiment will be denoted by the same referencenumerals, and description thereof will be simplified or omitted.

FIG. 4 is a view showing an example of a liquid immersion member 4Baccording to the second embodiment. The second embodiment is a modifiedexample of the first embodiment. The characteristic part of the secondembodiment different from the first embodiment described above is thatconcave portions 53 and 54 are formed on at least a part of an innerside surface 32A, a gas supply port 37B for supplying the gas GD and anair supply port 55B for supplying the steam GW are disposed on the innersurface of a concave portion 53 that defines the concave portion 53, anda gas recovery port 39B for recovering the gas GD and the steam GW isdisposed on the inner surface of a concave portion 54 that defines theconcave portion 54.

In FIG. 4, the concave portion 53 is recessed so as to be away from anouter side surface 31A facing the inner side surface 32A. The concaveportion 53 is disposed around the outer side surface 31A. The concaveportion 54 is disposed above the concave portion 53. The concave portion54 is recessed so as to be away from the outer side surface 31A facingthe inner side surface 32A. The concave portion 54 is disposed aroundthe outer side surface 31A.

The gas supply port 37B is disposed on the inner surface of the concaveportion 53. The gas supply port 37B supplies the gas GD to the space S2between the outer side surface 31A and the inner side surface 32A. Theair supply port 55B supplies the steam GW of the liquid LQ to the spaceS2 and makes the humidity of the space S2 supplied with the gas GDhigher than the humidity of the inner space 8.

In the present embodiment, since the concave portions 53 and 54 areformed, it is possible to increase the size of the space S2 in which thegas GD is filled. Thus, the gas GD in the space S2 can be smoothlydissolved in the liquid LQ, and charging can be suppressed. Moreover,since the steam GW is supplied to the space S2, dissolution of the gasGD in the liquid LQ is accelerated, and charging of the liquid LQ can besuppressed more effectively. Furthermore, since vaporization of theliquid LQ in the vicinity of the interface LG2 of the liquid LQ issuppressed, it is possible to suppress a change in the temperature ofthe liquid LQ, the terminating optical element 22, and the liquidimmersion member 4B.

In the second embodiment, although the gas supply port 37B and the airsupply port 55B are disposed in the concave portion 53, one of them maybe disposed in the concave portion 53, and the other may be disposed onthe inner side surface 32A on the outer side of the concave portion 53.

Moreover, the concave portion 53 may not be provided, and the gas supplyport 37B and the air supply port 55B may be disposed on the inner sidesurface 32A. Moreover, the concave portion 54 may not be provided, andthe gas recovery port 39B may be disposed on the inner side surface 32A.

Furthermore, in the second embodiment, at least one of the gas supplyport 37B, the gas recovery port 39B, and the air supply port 55B may beprovided on the upper surface 32B of the liquid immersion member 4B.

Third Embodiment

Next, the third embodiment will be described. In the followingdescription, constituent elements which are the same as or similar tothose of the above embodiments will be denoted by the same referencenumerals, and description thereof will be simplified or omitted.

FIG. 5 is a view showing an example of a liquid immersion member 4Caccording to the third embodiment. The third embodiment is a modifiedexample of the first embodiment. The characteristic part of the thirdembodiment different from the first embodiment described above is that agas supply port 36C, an air supply port 45C, and a gas recovery port 38Care disposed in at least a part of the circumference of the optical pathK of the exposure light EL and on a holding member 56 disposed on theouter side of the liquid immersion member 4C in the radiation directionin relation to the optical axis AX.

In the present embodiment, the holding member 56 is an annular memberdisposed around the liquid immersion member 4C. The holding member 56includes a lower surface 57 which is configured to face the surface ofthe substrate P. In the present embodiment, at least some of the gas GDsupplied from the gas supply port 36C is held between the lower surface57 of the holding member 56 and the surface of the substrate P.

In the present embodiment, a liquid supply port 35C for supplying theliquid LQ in order to fill the optical path K of the exposure light ELwith the liquid LQ, a liquid recovery port 40C (a porous member 41C) forrecovering the liquid LQ, a gas supply port 37C for supplying the gas GDto the space S2, and a gas recovery port 39C for recovering the gas GDin the space S2 are disposed in the liquid immersion member 4C.

In the present embodiment, a gas supply port 36C for supplying the gasGD to the space S1, an air supply port 45C for supplying the steam GW tothe space S1, and a gas recovery port 38C for recovering the gas GD andthe steam GW in the space S1 are disposed on the lower surface 57 of theholding member 56. The gas supply port 36C and the air supply port 45Care disposed on the inner surface of a concave portion 42C formed on thelower surface 57, and the gas recovery port 38C is disposed on the innersurface of a concave portion 43C formed on the lower surface 57. In thepresent embodiment, the space S1 is a space between at least a part ofthe lower surface 30C of the liquid immersion member 4C and the lowersurface 57 of the holding member 56, and the surface of the substrate P.

In the present embodiment, it is possible to suppress charging of theliquid LQ and the like and to suppress the occurrence of exposuredefects.

In the present embodiment, the gas supply port 36C and the air supplyport 45C may be disposed in the liquid immersion member 4C, and the gasrecovery port 38C may be disposed on the holding member 56. That is,some of the gas supply port 36C, the air supply port 45C, and the gasrecovery port 38C may be disposed on the holding member 56, and theremaining ports may be disposed in the liquid immersion member 4C.Moreover, some of the gas supply port 36C, the air supply port 45C, andthe gas recovery port 38C may be disposed on still another member.

Moreover, in the third embodiment, one of the gas supply port 36C andthe air supply port 45C may be disposed in the concave portion 42C, andthe other may be disposed on the lower surface 57 of the holding member56. The concave portion 42C may not be provided, and both the gas supplyport 36C and the air supply port 45C may be provided on the lowersurface 57. Moreover, in the third embodiment, the concave portion 43Cmay not be provided, and the gas recovery port 38C may be provided onthe lower surface 57. Furthermore, in the third embodiment, thehumidified gas GD may be supplied from the gas supply port 36C, and theair supply port 45C may be omitted. In the third embodiment, the steamof the liquid LQ may be supplied to the space S2, and the humidified gasGD may be supplied from the gas supply port 37C.

In the first to third embodiments described above, although a case wherethe steam GW humidifies the gas GD by the steam of the liquid LQ hasbeen described as an example, the gas GD may be humidified by the steamof liquid different from the liquid LQ.

Moreover, in the first to third embodiments described above, althoughthe gas GD supplied to the space S1 from the gas supply port is the sameas the gas GD supplied to the space S2 from the gas supply port, theymay be different from each other. For example, the gas GD supplied tothe space S1 may include carbon dioxide as the material that changes thespecific resistance of the liquid LQ, and the gas GD supplied to thespace S2 may include hydrogen as the material that changes the specificresistance of the liquid LQ. Alternatively, the concentration(proportion) of the material that changes the specific resistance of theliquid LQ may be different between that in the gas GD supplied to thespace S1 and that in the gas GD supplied to the space S2.

Furthermore, in the first to third embodiments described above, the gasincluding the material that changes the specific resistance of theliquid LQ may be supplied to any one of the spaces S1 and S2. Moreover,in the first to third embodiments described above, although at least apart of the space S1 is humidified by supplying the steam GW from theair supply port and/or supplying the humidified gas GD from the gassupply port, the space S1 may not be humidified. Furthermore, in thefirst to third embodiments described above, at least one of the gasrecovery port for recovering the gas from the space S1 and the gasrecovery port for recovering the gas from the space S2 may be omitted.

Fourth Embodiment

Next, the fourth embodiment will be described. In the followingdescription, constituent elements which are the same as or similar tothose of the above embodiments will be denoted by the same referencenumerals, and description thereof will be simplified or omitted.

FIG. 6 is a view showing an example of a liquid immersion member 4Daccording to the fourth embodiment. In FIG. 6, the liquid immersionmember 4D includes a first supply port 35D for supplying a first liquidLQ1 in order to fill the optical path K of the exposure light EL emittedfrom the emission surface 23 with the first liquid LQ1 having a firstspecific resistance and a second supply port 36D for supplying a secondliquid LQ2 having a specific resistance different from the first liquidLQ1 to at least a part of a space S11 around a liquid immersion spaceLS1 formed by the first liquid LQ1. In the present embodiment, thesecond liquid LQ2 has a specific resistance lower than the first liquidLQ1.

Similarly to the liquid immersion member 4 of the first embodimentdescribed above, the liquid immersion member 4D according to the presentembodiment is disposed in at least a part of the circumference of theoptical path K. A part of the liquid immersion space LS1 is formedbetween the substrate P facing the lower surface 30D of the liquidimmersion member 4D and the lower surface 30D of the liquid immersionmember 4D.

The first supply port 35D supplies the first liquid LQ1 to the spacebetween the emission surface 23 and the upper surface 33. In the presentembodiment, the first liquid LQ1 is water (pure water).

The second supply port 36D is disposed on the lower surface 30D of theliquid immersion member 4D. The second supply port 36D supplies thesecond liquid LQ2 to the space S11. In the present embodiment, thesecond liquid LQ2 includes the first liquid LQ1. That is, the maincomponent of the second liquid LQ2 is the first liquid LQ1 (water).

In the present embodiment, the second liquid LQ2 is formed by dissolving(adding) a material that decreases the specific resistance of the firstliquid LQ1 in the first liquid LQ1. In the present embodiment, thematerial is carbon dioxide. That is, the second liquid LQ2 is carbonatedwater which is formed by dissolving carbon dioxide in the first liquidLQ1 (water).

The second liquid LQ2 may include ozone or hydrogen. That is, the secondliquid LQ2 may be ozone water in which ozone is dissolved in water andmay be hydrogen water in which hydrogen is dissolved in water. The ozonewater or the hydrogen water can decrease the specific resistance of thefirst liquid LQ1.

Moreover, the liquid immersion member 4D includes a first recovery port40D that is disposed on the lower surface 30D so as to recover at leastsome of the first liquid LQ1 on the substrate P. A porous member 41D isdisposed in the first recovery port 40D. The first recovery port 40D ofthe liquid immersion member 4D has approximately the same configurationas the liquid recovery port 40 of the liquid immersion member 4 of thefirst embodiment described above, and detailed description thereof willbe omitted.

The second supply port 36D is disposed on the outer side of the firstrecovery port 40D in the radiation direction in relation to the opticalaxis AX. In the present embodiment, the shape of the second supply port36D within the XY plane is annular. The second supply port 36D isdisposed so as to surround the first recovery port 40D. In addition, aplurality of second supply ports 36D may be disposed on the lowersurface 30D around the optical path K at predetermined intervals.

Moreover, the liquid immersion member 4D includes a second recovery port58D that is disposed on the lower surface 30D so as to recover at leastsome of the second liquid LQ2 on the substrate P. The second recoveryport 58D is disposed on the outer side of the second supply port 36D inthe radiation direction in relation to the optical axis AX. A porousmember 59D is disposed in the second recovery port 58D. Similarly to thefirst recovery port 40D, the second recovery port 58D recovers onlyliquid through the openings or pores of the porous member 59 but doesnot recover gas.

Moreover, the liquid immersion member 4D includes a gas supply port 37Dwhich is disposed on the inner side surface 32A so as to be capable ofsupplying gas GD including a material capable of changing the specificresistance of the first liquid LQ1 to the space S2 between theterminating optical element 22 and the liquid immersion member 4D and agas recovery port 39D capable of recovering the gas GD in the space S2.The gas supply port 37D and the gas recovery port 39D of the liquidimmersion member 4D have approximately the same configurations as thegas supply port 37 and the gas recovery port 39D of the liquid immersionmember 4 of the first embodiment described above, and detaileddescription thereof will be omitted.

Next, a method of exposing the substrate P using the exposure apparatusEX having the configuration described above will be described.

The control device 7 performs the operation of supplying the firstliquid LQ1 by the first supply port 35D and the operation of recoveringliquid by the first recovery port 40D in a state where the emissionsurface 23 and the lower surface 30D face the surface of the substrateP. The first supply port 35D supplies the first liquid LQ1 to theoptical path K of the exposure light EL. At least some of the firstliquid LQ1 between the lower surface 30D and the surface of thesubstrate P is recovered through the first recovery port 40D. A liquidimmersion space LS1 is formed by the first liquid LQ1 supplied from thefirst supply port 35D so that the optical path K of the exposure lightEL between the emission surface 23 and the surface of the substrate P isfilled with the first liquid LQ1.

Moreover, the control device 7 performs the operation of supplying thegas GD to the space S2 by the gas supply port 37D and the operation ofrecovering the gas GD in the space S2 by the gas recovery port 39D. Inthis way, the space S2 is filled with the gas GD, and the gas GD comesinto contact with the interface LG2 of the first liquid LQ1.

Moreover, the control device 7 performs the operation of supplying thesecond liquid LQ2 to the space S11 by the second supply port 36D andperforms the operation of recovering the second liquid LQ2 in the spaceS11 by the second recovery port 58D. At least some of the second liquidLQ2 supplied to the space S11 through the second supply port 36D isrecovered through the first recovery port 40D. Moreover, at least someof the second liquid LQ2 supplied to the space S11 through the secondsupply port 36D is recovered through the second recovery port 58D. Thatis, in the present embodiment, the first recovery port 40D recovers thefirst and second liquid LQ1 and LQ2 on the substrate P, and the secondrecovery port 58D mainly recovers the second liquid LQ2 on the substrateP.

In this way, the space S11 is filled with the second liquid LQ2, and thesecond liquid LQ2 supplied to the space S11 through the second supplyport 36D comes into contact with the interface LG1 of the first liquidLQ1 in the liquid immersion space LS1.

The control device 7 starts exposure of the substrate P in a state wherethe liquid immersion space LS1 is formed. The control device 7 exposesthe substrate P with the exposure light EL from the emission surface 23via the first liquid LQ1 between the emission surface 23 and the surfaceof the substrate P.

During exposure of the substrate P, the operation of supplying the firstliquid LQ1 by the first supply port 35D, the operation of supplying thesecond liquid LQ2 by the second supply port 36D, the operation ofrecovering the first and second liquid LQ1 and LQ2 by the first recoveryport 40D, the operation of recovering the second liquid LQ2 by thesecond recovery port 58D, the operation of supplying the gas GD by thegas supply port 37D, and the operation of recovering the gas GD by thegas recovery port 39D are executed concurrently.

In the present embodiment, the space S1 around the liquid immersionspace LS1 formed by the first liquid LQ1 is filled with the secondliquid LQ2 having a low specific resistance, and the space S11 filledwith the second liquid LQ2 suppress the first liquid LQ1 in the liquidimmersion space LS1 from coming into contact with the gas (air in thepresent embodiment) in the inner space 8 controlled by the chamberdevice 5.

In the present embodiment, since the second liquid LQ2 which has a lowerspecific resistance than the first liquid LQ1 and which is mixed withthe first liquid LQ1 in the vicinity of the interface LG1 and is capableof decreasing the specific resistance of the first liquid LQ1 in thevicinity of the interface LG1 is supplied to the space S11, charging ofthe first liquid LQ1 is suppressed. Moreover, charging of the liquidimmersion member 4 contacting the first liquid LQ1, charging of thesubstrate P, and charging of the substrate stage 2 (the plate member T)are suppressed.

Fifth Embodiment

Next, the fifth embodiment will be described. In the followingdescription, constituent elements which are the same as or similar tothose of the above embodiments will be denoted by the same referencenumerals, and description thereof will be simplified or omitted.

FIG. 7 is a view showing an example of a liquid immersion member 4Eaccording to the fifth embodiment. The liquid immersion member 4Eaccording to the fifth embodiment is a modified example of the liquidimmersion member 4D according to the fourth embodiment. Thecharacteristic part of the liquid immersion member 4E according to thefifth embodiment different from the liquid immersion member 4D accordingto the fourth embodiment is that a second supply port 36E for supplyingthe second liquid LQ2 is disposed on the inner side of a first recoveryport 40E in the radiation direction in relation to the optical axis AX.Moreover, in the liquid immersion member 4E of the present embodiment,the second recovery port (58D) is not provided.

In the present embodiment, the second supply port 36E is disposed on thelower surface 30E of the liquid immersion member 4E around the opticalpath K. That is, the shape of the second supply port 36E is annular. Inaddition, a plurality of second supply ports 36E may be disposed on thelower surface 30E around the optical path K at predetermined intervals.

Moreover, the liquid immersion member 4E includes a gas supply port 37Efor supplying the gas GD to the space S2 and a gas recovery port 39E forrecovering the gas GD in the space S2. The gas supply port 37E and thegas recovery port 39E of the liquid immersion member 4E haveapproximately the same configurations as the gas supply port 37 and thegas recovery port 39D of the liquid immersion member 4 of the firstembodiment described above, and detailed description thereof will beomitted.

In the present embodiment, the optical path K is formed by the firstliquid LQ1, and the periphery of a liquid immersion space LS2 includingan interface LG11 between the liquid immersion member 4E and thesubstrate P is formed by the first liquid LQ1 from the first supply port35E and the second liquid LQ2 from the second supply port 36E. The firstrecovery port 40E recovers both the first liquid LQ1 and the secondliquid LQ2 through a porous member 41E.

In the present embodiment, since the second liquid LQ2 having a lowerspecific resistance than the first liquid LQ1 is supplied in thevicinity of the interface LG11, it is possible to effectively suppresscharging of the liquid in the liquid immersion space LS in the vicinityof the interface LG11.

In the present embodiment, a second recovery port disposed to beseparated from the first recovery port 40E may be provided on the lowersurface 30E of the liquid immersion member 4E on the outer side of thefirst recovery port 40E in the radiation direction in relation to theoptical axis AX.

Moreover, in the present embodiment, an air supply port for supplyingthe steam of the second liquid LQ2 may be provided on the outer side ofthe first recovery port 40E in the radiation direction in relation tothe optical axis AX, and similarly to the first to third embodimentsdescribed above, a space having higher humidity than the inner space 8may be formed in at least a part of the circumference of the liquidimmersion space LS2.

Sixth Embodiment

Next, the sixth embodiment will be described. In the followingdescription, constituent elements which are the same as or similar tothose of the above embodiments will be denoted by the same referencenumerals, and description thereof will be simplified or omitted.

FIG. 8 is a view showing an example of a liquid immersion member 4Faccording to the sixth embodiment. The sixth embodiment is a modifiedexample of the fourth embodiment. The characteristic part of the sixthembodiment different from the fourth embodiment is that a second supplyport 36F and a second recovery port 58F (a porous member 59F) aredisposed in at least a part of the circumference of the optical path Kof the exposure light EL and on a holding member 56F disposed on theouter side of the liquid immersion member 4F in the radiation directionin relation to the optical axis AX.

In the present embodiment, the holding member 56F is an annular memberdisposed around the liquid immersion member 4F. The holding member 56Fincludes a lower surface 57F which is configured to face the surface ofthe substrate P. In the present embodiment, at least some of the secondliquid LQ2 is held between the lower surface 57F of the holding member56F and the surface of the substrate P.

In the present embodiment, a first supply port 35F for supplying thefirst liquid LQ1 to the optical path K, a first recovery port 40F inwhich the porous member 41F is disposed and which recovers the liquid onthe substrate P, a gas supply port 37F for supplying the gas GD to thespace S2, and a gas recovery port 39F for recovering the gas GD in thespace S2 are disposed in the liquid immersion member 4F.

In the present embodiment, a second supply port 36F for supplying thesecond liquid LQ2 to the space S11 and a second recovery port 58F forrecovering at least some of the second liquid LQ2 are disposed on thelower surface 57F of the holding member 56F. The second recovery port58F recovers the second liquid LQ2 through a porous member 59F. Thesecond recovery port 58F is disposed on the outer side of the secondsupply port 36F in the radiation direction in relation to the opticalaxis AX. The second recovery port 58F mainly recovers the second liquidLQ2 from the second supply port 36F, and the first recovery port 40Frecovers the first liquid LQ1 from the first supply port 35F and thesecond liquid LQ2 from the second supply port 36F.

In the present embodiment, it is possible to suppress charging of thefirst liquid LQ1 and the like and to suppress the occurrence of exposuredefects.

In the present embodiment, the second supply port 36F may be disposed onthe holding member 56F, and the second recovery port 58F may be disposedon a member different from the liquid immersion member 4F and theholding member 56F.

Seventh Embodiment

Next, the seventh embodiment will be described. In the followingdescription, constituent elements which are the same as or similar tothose of the above embodiments will be denoted by the same referencenumerals, and description thereof will be simplified or omitted.

FIG. 9 is a view showing an example of a liquid immersion member 4Gaccording to the seventh embodiment. The seventh embodiment is amodified example of the sixth embodiment.

As shown in FIG. 9, a second supply port 36G for supplying the secondliquid LQ2 to the space S11 is provided on the lower surface 30G of theliquid immersion member 4G. Moreover, the liquid immersion member 4Gincludes a first supply port 35G for supplying the first liquid LQ1 tothe optical path K, a gas supply port 37G for supplying the gas GD tothe space S2, a gas recovery port 39G for recovering the gas GD in thespace S2, and a first recovery port 40G for recovering the liquid on thesubstrate P.

In the present embodiment, a second recovery port 58G for recovering atleast some of the second liquid LQ2 is provided on the lower surface 57Gof the holding member 56G.

In the present embodiment, it is possible to suppress charging of thefirst liquid LQ1 and the like and to suppress the occurrence of exposuredefects.

In the fourth to seventh embodiments described above, although a casewhere the second liquid LQ2 is formed by dissolving the material thatdecreases the specific resistance of the first liquid LQ1 in the firstliquid LQ1 has been described as an example, the second liquid LQ2 maybe formed by dissolving the material in a liquid different from thefirst liquid LQ1. That is, the main component of the first liquid LQ1may be different from the main component of the second liquid LQ2.

Moreover, in the fourth to seventh embodiments described above, thematerial that decreases the specific resistance of the first liquid LQ1included in the second liquid LQ2 may be different from the materialthat decreases the specific resistance of the first liquid LQ1 includedin the gas GD supplied to the space S2.

Moreover, in the fourth to seventh embodiments described above, the gasrecovery port (39D, 39E, 39F, or 39G) for recovering the gas from thespace S2 may be provided on the upper surface 32 of the liquid immersionmember (4D, 4E, 4F, or 4G), and the gas recovery port (39D, 39E, 39F, or39G) may not be provided.

Moreover, in the fourth to seventh embodiments described above, thesteam of the first liquid LQ1 may be supplied to the space S2, and thegas GD humidified by the steam of the first liquid LQ1 may be suppliedto the space S2.

Moreover, in the fourth to seventh embodiments described above, the gassupply port (37D, 37E, 37F, or 37G) for supplying the gas GD to thespace S2 and the gas recovery port (39D, 39E, 39F, or 39G) forrecovering the gas from the space S2 may be omitted.

Moreover, in the fourth, sixth and seventh embodiments described above,an air supply port for supplying the steam of the second liquid LQ2 maybe provided on the outer side of the second recovery port (58D, 58F, or58G) in the radiation direction in relation to the optical axis AX, andsimilarly to the first to third embodiments described above, a space ofwhich the humidity is higher than the inner space 8 may be formed in atleast a part of the circumference of the space S11.

Moreover, in the fourth, sixth, and seventh embodiments described above,although the difference between the pressure of the upper surface-sidespace of the porous member (59D, 59F, or 59G) and the pressure of thelower surface-side space is adjusted so that the second recovery port(58D, 58F, or 58G) recovers only liquid, the second recovery port (58D,58F, or 58G) may recover liquid together with gas. In this case, theporous member (59D, 59F, or 59G) may be omitted.

Moreover, in the fourth, sixth, and seventh embodiments described above,the second recovery port (the porous member) may be disposed on thelower side than the first recovery port (the porous member).

Moreover, in the first to seventh embodiments described above, althoughthe first recovery port (40 or the like) recovers only liquid, the firstrecovery port may recover liquid together with gas. In this case, theporous member (41 or the like) of the first recovery port (40 or thelike) may be omitted.

Moreover, in the first to seventh embodiments described above, theliquid immersion member (4 or the like) may be movable relative to theterminating optical element 22 in parallel to at least one of the X, Y,and Z axes and may be rotatable about the X, Y, and Z axes.

Moreover, in the first to seventh embodiments described above, the plateportion 41 of the liquid immersion member may be omitted. For example,the lower surface (30 or the like) of the liquid immersion member may beprovided in at least a part of the circumference of the emission surface23. In this case, the lower surface (30 or the like) of the liquidimmersion member may be disposed at the same height as the emissionsurface 23 or on the upper side (+Z side) than the emission surface 23.

Moreover, in the first to seventh embodiments described above, althoughthe optical path on the emission side (image plane side) of theterminating optical element 22 of the projection optical system PL isfilled with the liquid LQ (the first liquid LQ1), a projection opticalsystem in which the optical path on the incidence side (object planeside) of the terminating optical element 22 is also filled with liquidmay be employed as disclosed in the pamphlet of PCT InternationalPublication No. 2004/019128, for example. The liquid filled in theincidence-side optical path of the terminating optical element 22 may bethe same kind of liquid as the liquid LQ (the first liquid LQ1) and maybe a different kind of liquid from the liquid LQ (the first liquid LQ1).

Although the liquid LQ (the first liquid LQ1) of the respectiveembodiments described above is water, it may be liquid other than water.For example, hydrofluoroether (HFE), perfluorinated polyether (PFPE),fomblin oil, or the like can be used as the liquid LQ (the first liquidLQ1). Moreover, various liquids, for example a supercritical liquid, canbe used as the liquid LQ.

Furthermore, the substrate P of the respective embodiments describedabove may be not only a semiconductor wafer for manufacturingsemiconductor devices but also a glass substrate for display devices, aceramic wafer for thin-film magnetic heads, or the raw plate (syntheticquartz or a silicon wafer) of a mask or a reticle that is used by anexposure apparatus.

As for the exposure apparatus EX, a step-and-scan type scanning exposureapparatus (a scanning stepper) that scans and exposes the pattern of themask M by synchronously moving the mask M and the substrate P, and astep-and-repeat type projection exposure apparatus (a stepper) thatperforms exposure of the pattern of the mask M in a batch with the maskM and the substrate P in a stationary state and then sequentially movesthe substrate P in a stepwise manner can be used.

Furthermore, the step-and-repeat type exposure may be performed in abatch such that after a reduced image of a first pattern is transferredto the substrate P using the projection optical system in a state wherethe first pattern and the substrate P are substantially stationary, areduced image of a second pattern is transferred to the substrate P soas to be partially superimposed on the first pattern using theprojection optical system in a state where the second pattern and thesubstrate P are are substantially stationary (a stitch type batchexposure apparatus). In addition, a step-and-stitch type exposureapparatus in which at least two patterns are transferred to thesubstrate P in a partially superimposed manner, and the substrate P issequentially moved can be used as the stitch type exposure apparatus.

Moreover, as disclosed in U.S. Pat. No. 6,611,316, for example, thepresent invention can also be applied to an exposure apparatus thatcombines the patterns of two masks on a substrate through a projectionoptical system and double exposes, substantially simultaneously, asingle shot region on the substrate using a single scanning exposure.Furthermore, the present invention can also be applied to a proximitytype exposure apparatus, a mirror projection aligner, or the like.

Moreover, the present invention can also be adapted to a twin stage typeexposure apparatus that includes a plurality of substrate stages, asdisclosed in the specifications of U.S. Pat. Nos. 6,341,007, 6,208,407,and 6,262,796, for example.

In addition, the present invention can also be applied to an exposureapparatus that includes a substrate stage which holds a substrate and ameasurement stage on which a reference member having a reference markformed thereon and/or various photoelectric sensors are mounted, andwhich does not hold an exposure target substrate, as disclosed in thespecification of U.S. Pat. No. 6,897,963 and the specification of USPatent Application Publication No. 2007/0127006, for example. Moreover,the present invention can also be applied to an exposure apparatus thatincludes a plurality of substrate stages and a plurality of measurementstages.

The type of exposure apparatus EX is not limited to an exposureapparatus for manufacturing semiconductor devices that exposes thepattern of a semiconductor device on the substrate P, but can be widelyapplied to exposure apparatuses used for manufacturing liquid crystaldisplay devices or displays and exposure apparatuses used formanufacturing thin-film magnetic heads, image capturing devices (CCDs),micromachines (MEMS), DNA chips, or reticles and masks, for example.

Moreover, in the respective embodiments described above, an ArF excimerlaser may be used as a light source apparatus that generates ArF excimerlaser light as the exposure light EL. However, as disclosed in U.S. Pat.No. 7,023,610, for example, a harmonic generation device which includesa solid-state laser light source such as a DFB semiconductor laser or afiber laser, an optical amplifier part including a fiber amplifier andthe like, and a wavelength converter, and which outputs pulsed lightwith a wavelength of 193 nm may be used. Furthermore, in the aboveembodiments, although the illumination regions and projection regionsdescribed above have a rectangular shape, they may have a differentshape, for example, a circular arc shape.

Furthermore, in the respective embodiments described above, atransmitting mask in which a predetermined shielding pattern (or a phasepattern or a dimming pattern) is formed on a transmissive substrate hasbeen used. However, instead of this mask, as disclosed in thespecification of U.S. Pat. No. 6,778,257, for example, a variable formmask (also referred to as an electronic mask, an active mask, or animage generator) that forms a transmission pattern, a reflectionpattern, or a light emitting pattern based on electronic data of thepattern to be exposed may be used. The variable form mask includes adigital micro-mirror device (DMD), which is one kind of non-emissiontype image display device (spatial light modulator), for example. Inaddition, instead of a variable form mask that includes a non-emissiontype image display device, a pattern forming apparatus that includes aself-emission image display device may be provided. Examples of theself-emission type image display device include a cathode ray tube(CRT), an inorganic EL display, an organic EL display (OLED: organiclight emitting diode), an LED display, an LD display, a field emissiondisplay (FED), and a plasma display (PDP: plasma display panel).

In the respective embodiments described above, although the exposureapparatus that includes the projection optical system PL has beendescribed as an example, the present invention can be applied to anexposure apparatus and an exposure method which do not use theprojection optical system PL. As above, even when the projection opticalsystem PL is not used, the exposure light is irradiated onto thesubstrate through optical members such as lenses, and a liquid immersionspace is formed in a predetermined space between these optical membersand the substrate.

Furthermore, as disclosed in the pamphlet of PCT InternationalPublication No. 2001/035168, for example, the present invention can bealso applied to an exposure apparatus (a lithography system) thatexposes the substrate P with a line-and-space pattern by forminginterference fringes on the substrate P.

As described above, the exposure apparatus EX of the present embodimentis manufactured by assembling various subsystems including therespective constituent elements mentioned in the claims of the presentapplication so that predetermined mechanical, electrical, and opticalaccuracies are maintained. To ensure these various accuracies,adjustments are performed before and after this assembly, including anadjustment for achieving optical accuracy for various optical systems,an adjustment for achieving mechanical accuracy for various mechanicalsystems, and an adjustment for achieving electrical accuracy for variouselectrical systems. The process of assembling various subsystems intothe exposure apparatus includes, for example, the mechanicalinterconnection of various subsystems, the wiring and connection of thecircuits, and the piping and connection of the atmospheric pressurecircuit. Naturally, prior to performing the process of assemblingvarious subsystems into the exposure apparatus, the processes ofassembling individual subsystems are performed. When the process ofassembling various subsystems into the exposure apparatus is completed,comprehensive adjustments are performed, whereby various accuracies ofthe exposure apparatus as a whole are secured. Furthermore, it ispreferable to manufacture the exposure apparatus in a clean room wherethe temperature, the cleanliness level, and the like are controlled.

As shown in FIG. 10, a microdevice such as a semiconductor device ismanufactured through: a step 201 of designing the functions andperformance of the microdevice; a step 202 of fabricating a mask (areticle) based on this designing step; a step 203 of manufacturing asubstrate which is the base material of the device; a substrateprocessing step 204 including exposing the substrate with exposure lightusing the pattern of the mask in accordance with the embodimentsdescribed above and developing the exposed substrate; a deviceassembling step 205 (including a processing process such as a dicingprocess, a bonding process, and a packaging process); an inspecting step206; and the like.

Furthermore, the requirements of the respective embodiments may beappropriately combined with each other. Moreover, some constituentelements may not be used. As far as is permitted by the law, thedisclosures in all of the patent application Publications and US patentsrelated to exposure apparatuses and the like cited in the aboverespective embodiments and modified examples, are incorporated herein byreference.

What is claimed is:
 1. An exposure apparatus that exposes a substratewith exposure light via a liquid, the exposure apparatus comprising: anoptical system having a terminating optical element that emits theexposure light into an optical path; a liquid supply port via which theliquid is supplied to fill the optical path of the exposure light withthe liquid; a liquid recovery port; and a fluid supply port thatsupplies carbon dioxide gas to a space, the space at least partlysurrounding the optical path, wherein: the liquid recovery port isdisposed such that an upper surface of the substrate faces the liquidrecovery port, and the fluid supply port is disposed radially outward ofthe liquid recovery port in a radial direction in relation to an opticalaxis of the optical system.
 2. The exposure apparatus according to claim1, further comprising a fluid recovery port.
 3. The exposure apparatusaccording to claim 2, wherein the fluid recovery port is disposedradially outward of the fluid supply port in a radial direction inrelation to the optical axis of the optical system.
 4. The exposureapparatus according to claim 3, wherein the fluid supply port isdisposed between the liquid recovery port and the fluid recovery port ina radial direction in relation to the optical axis of the opticalsystem.
 5. The exposure apparatus according to claim 4, wherein thefluid supply port and the fluid recovery port face the space, the spacebeing substantially filled with gas.
 6. The exposure apparatus accordingto claim 4, wherein the fluid supply port and the fluid recovery portface the upper surface of the substrate during exposure of thesubstrate.
 7. The exposure apparatus according to claim 1, furthercomprising a liquid immersion member disposed radially outward of theoptical path in relation to the optical axis of the optical system,wherein the liquid is supplied to form a liquid immersion space suchthat a part of the liquid immersion space is formed between an objectfacing the liquid immersion member and the liquid immersion member. 8.The exposure apparatus according to claim 7, wherein the liquidimmersion member has the liquid recovery port and the fluid supply port.9. The exposure apparatus according to claim 8, further comprising afluid recovery port, the liquid immersion member has the fluid recoveryport.
 10. The exposure apparatus according to claim 9, wherein the fluidrecovery port is disposed radially outward of the fluid supply port in aradial direction in relation to the optical axis of the optical system.11. The exposure apparatus according to claim 8, wherein furthercomprising a fluid recovery port disposed radially outward of the fluidsupply port in a radial direction in relation to the optical axis of theoptical system.
 12. The exposure apparatus according to claim 10,wherein the liquid immersion member has the liquid supply port.
 13. Theexposure apparatus according to claim 7, further comprising an outermember that is disposed radially outward of the optical path andradially outward of the liquid immersion member in a radial direction inrelation to the optical axis of the optical system.
 14. The exposureapparatus according to claim 13, wherein the liquid immersion member hasthe liquid recovery port and the outer member has the fluid supply port.15. The exposure apparatus according to claim 14, further comprising afluid recovery port which is disposed radially outward of the fluidsupply port in a radial direction in relation to the optical axis of theoptical system.
 16. The exposure apparatus according to claim 15,wherein the outer member has the fluid recovery port.
 17. The exposureapparatus according to claim 14, wherein the liquid immersion member hasthe liquid supply port.
 18. The exposure apparatus according to claim16, wherein the liquid immersion member has the liquid supply port. 19.The exposure apparatus according to claim 1, wherein the terminatingoptical element has an emission surface and an outer surface extendingupwardly with respect to the emission surface, and the liquid supplyport faces the outer surface.
 20. The exposure apparatus according toclaim 1, wherein the space is disposed such that at least some of thecarbon dioxide gas in the space is able to contact the liquid.
 21. Theexposure apparatus according to claim 1, wherein the carbon dioxide gasis capable of decreasing the specific resistance of the liquid.
 22. Theexposure apparatus according to claim 1, wherein the carbon dioxide gassupplied to the space is dissolved in a fluid.
 23. The exposureapparatus according to claim 1, wherein the carbon dioxide gas suppliedto the space is mixed with at least one additional gas.
 24. A devicemanufacturing method comprising: exposing a substrate using the exposureapparatus according to claim 1; and developing the exposed substrate.25. A method of exposing a substrate with exposure light, the methodcomprising: supplying a liquid to an optical path of the exposure lightwith a liquid supply port; removing at least some of the liquid in theoptical path with a liquid recovery port; and supplying carbon dioxidegas to a space with a fluid supply port, the space at least partiallysurrounding the optical path, wherein: the liquid recovery port isdisposed such that an upper surface of the substrate faces the liquidrecovery port, and the fluid supply port is disposed radially outward ofthe liquid recovery port in a radial direction in relation to an opticalaxis.
 26. The method according to claim 25, wherein the liquid recoveryport sucks the liquid in order remove the liquid from the optical path.27. The method according to claim 25, further comprising removing atleast some of the carbon dioxide gas from the space with a fluidrecovery port.
 28. The method according to claim 27, wherein the fluidrecovery port is disposed radially outward of the fluid supply port in aradial direction in relation to the optical axis.
 29. The methodaccording to claim 28, wherein the fluid supply port is disposed betweenthe liquid recovery port and the fluid recovery port in a radialdirection in relation to the optical axis.
 30. The method according toclaim 27, wherein: the space is substantially filled with gas, and thefluid supply port and the fluid recovery port face the space.
 31. Themethod according to claim 25, wherein at least some of the carbondioxide gas contacts the liquid in the optical space and decreases thespecific resistance of the liquid.
 32. The method according to claim 25,wherein the carbon dioxide gas supplied to the space is dissolved in afluid.
 33. The method according to claim 25, wherein the carbon dioxidegas supplied to the space is mixed with at least one additional gas.